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Mineral and crystal chemical study of pseudo-C2/m non-metamict chevkinite-(Ce): An investigation into the intracrystalline distribution of LREE, HREE, and octahedral cations in samples from the Azores and Pakistan

  • Susanna Carbonin , Filippo Ridolfi , Alberto Renzulli , Elena Belluso , Luca Nodari , Federica Liziero and Silvana Capella
Published/Copyright: May 4, 2024
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American Mineralogist
From the journal American Mineralogist Volume 109 Issue 5

Abstract

The cation distribution among the A, B, C, and D sites of 13 crystals of chevkinite-(Ce) by X-ray single-crystal diffraction and electron microprobe analyses is reported in this article. The general formula of chevkinite-(Ce) is A4BC2D2O8(Si2O7)2, where A = REE, Ca, Th, Sr; B = Fe, Mn, Mg; C = Fe, Ti, Nb, Zr, Mg, Al; and D = Ti. Ten crystals come from quartz-bearing syenite samples of Agua de Pau (Azores Islands), and three are euhedral chevkinite crystals of a quartz-bearing pegmatite from Tangir Valley, northwestern Pakistan. The real space group for these samples is P21/a, but the average structure in space group C2/m was used for structural refinement and further interpretation. Cation distribution was determined by minimization of the function fΣNσ2 that represents the sum of the squared numbers of standard deviation by which each expected quantity differs from the calculated one. Both X-ray diffraction and electron microprobe data were considered in minimization. Our results show that the two non-equivalent A sites are occupied dominantly by REE and Ca, distributed mainly as a function of their ionic size. Lanthanum enters only the 10-coordinated A2 site, whereas heavier and smaller REE enter only the 8-coordinated A1. Furthermore, comparison between bond valence sum and formal charge revealed highly stretched bonds for the A1 polyhedron, suggesting that bond lengths are too long for HREE. These findings can help better characterize the well-known ability of chevkinite to fractionate LREE from HREE. The Azores chevkinite is particularly enriched in Nb relative to its host rock. Our results show that Ti occupancy in the D sites can be as low as ca. 50% due to the presence of significant amounts of Nb, besides Fe and Zr. For two Azores crystals showing patchy zoning, a complex history of late-stage crystallization is inferred, with multiple events of Ca and REE enrichments. One of these crystals showed the best structure refinement, implying that late-magmatic to deuteric alteration stages did not affect its crystallinity. The CaO content of Azores chevkinites practically spans the entire chevkinite field in the chevkinite/perrierite CaO vs. FeO discrimination diagram. In addition, we identified possible structural stability limits that can be linked to the occupancy of the B site at high CaO, and of the C sites at high-FeO contents. The Pakistan chevkinites were also analyzed by Mössbauer spectroscopy. Only one Fe3+ component was identified, which occupies the C sites. Among the two ferrous doublets, the component with the highest isomeric shift value is Fe2+ entering the most distorted crystallographic site B, while the other, representative of a less distorted octahedral site, corresponds to Fe2+ entering the D sites.

Keywords: Chevkinite; crystal structure; non-metamict; deuteric alteration; Mössbauer spectroscopy

Acknowledgments

This paper is dedicated to the memory of Umberto Russo (University of Padova), who contributed to elucidate the MS spectrum of the chevkinites in the early days of this study. We fondly remember Umberto for his ability to transmit interest and curiosity.

The authors thank CNR-IGG for the maintenance of the electron microprobe laboratory in Padova. S.C. greatly acknowledges the expertise of Giorgio Menegazzo who wrote the minimization program and tested it with no regard of time. Anna Fioretti, Ferdinando Bosi, Ray Macdonald, Marcin Stachowicz, Francesco Princivalle, and Silvano Sommacal are warmly thanked for their help in various aspects that led to the development of this work. The late Renato Pagano and Vittorio Mattioli kindly provided the Pakistan chevkinite sample investigated in the present study. The authors are also very grateful to Federico Pezzotta (Museo di Storia Naturale, Milano, Italy) and to Umberto Righi, an Italian mineral collector, for the information given about the outcrop of the chevkinite host-rock along the Tangir Valley in northwestern Pakistan. We thank Raul Carampin (CNR-IGG, Padova) for his generous assistance with the microprobe analysis, and Sandra Boesso for heavy liquid concentrations of chevkinite minerals. Nikita Chukanov, an anonymous reviewer, and Lee Groat provided very detailed and helpful reviews of the manuscript. Editorial handling by Charles Geiger is gratefully acknowledged.

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Received: 2022-06-16
Accepted: 2023-07-23
Published Online: 2024-05-04
Published in Print: 2024-05-27

© 2024 by Mineralogical Society of America

Articles in the same Issue

  1. Perspectives
  2. Characterizing basalt-atmosphere interactions on Venus: A review of thermodynamic and experimental results
  3. Influence of crystallographic anisotropy on the electrical conductivity of apatite at high temperatures and high pressures
  4. Using pyrite composition to track the multi-stage fluids superimposed on a porphyry Cu system
  5. Geochemical discrimination of pyrite in diverse ore deposit types through statistical analysis and machine learning techniques
  6. Correlation between Si-Al disorder and hydrogen-bonding distance variation in ussingite (Na2AlSi3O8OH) revealed by one- and two-dimensional multi-nuclear NMR and first-principles calculation
  7. Single-crystal X-ray diffraction on the structure of (Al,Fe)-bearing bridgmanite in the lower mantle
  8. Multi-scale and multi-modal imaging study of mantle xenoliths and petrological implications
  9. Mineral and crystal chemical study of pseudo-C2/m non-metamict chevkinite-(Ce): An investigation into the intracrystalline distribution of LREE, HREE, and octahedral cations in samples from the Azores and Pakistan
  10. Evolution of layering in a migmatite sample: Implications for the petrogenesis of multidomain monazite and zircon
  11. Waipouaite, Ca3 (V4.54+V0.55+) O9[(Si2O5(OH)2][Si3O7.5(OH)1.5]·11H2O, a new polyoxovanadate mineral from the Aranga Quarry, New Zealand
  12. Scandio-winchite, ideally□(NaCa)(Mg4Sc)(Si8O22)(OH)2: The first Sc-dominant amphibole-supergroup mineral from Jordanów Śląski, Lower Silesia, southwestern Poland
  13. Znucalite, the only known zinc uranyl carbonate: Its crystal structure and environmental implications
  14. Presentation of the Dana Medal of the Mineralogical Society of America for 2023 to Razvan Caracas
  15. Acceptance of the Dana Medal of the Mineralogical Society of America for 2023
  16. Presentation of the Distinguished Public Service Award of the Mineralogical Society of America for 2024 to Sharon Tahirkheli
  17. Acceptance of the Distinguished Public Service Award of the Mineralogical Society of America for 2024
  18. Presentation of the Mineralogical Society of America Award for 2023 to Shaunna M. Morrison
  19. Acceptance of the Mineralogical Society of America Award for 2023
  20. Presentation of the 2023 Roebling Medal of the Mineralogical Society of America to Georges Calas
  21. Acceptance of the 2023 Roebling Medal of the Mineralogical Society of America
  22. Book Review
  23. Book Review: Cosmochemistry
https://doi.org/10.2138/am-2022-8658
Keywords for this article
Chevkinite; crystal structure; non-metamict; deuteric alteration; Mössbauer spectroscopy

Articles in the same Issue

  1. Perspectives
  2. Characterizing basalt-atmosphere interactions on Venus: A review of thermodynamic and experimental results
  3. Influence of crystallographic anisotropy on the electrical conductivity of apatite at high temperatures and high pressures
  4. Using pyrite composition to track the multi-stage fluids superimposed on a porphyry Cu system
  5. Geochemical discrimination of pyrite in diverse ore deposit types through statistical analysis and machine learning techniques
  6. Correlation between Si-Al disorder and hydrogen-bonding distance variation in ussingite (Na2AlSi3O8OH) revealed by one- and two-dimensional multi-nuclear NMR and first-principles calculation
  7. Single-crystal X-ray diffraction on the structure of (Al,Fe)-bearing bridgmanite in the lower mantle
  8. Multi-scale and multi-modal imaging study of mantle xenoliths and petrological implications
  9. Mineral and crystal chemical study of pseudo-C2/m non-metamict chevkinite-(Ce): An investigation into the intracrystalline distribution of LREE, HREE, and octahedral cations in samples from the Azores and Pakistan
  10. Evolution of layering in a migmatite sample: Implications for the petrogenesis of multidomain monazite and zircon
  11. Waipouaite, Ca3 (V4.54+V0.55+) O9[(Si2O5(OH)2][Si3O7.5(OH)1.5]·11H2O, a new polyoxovanadate mineral from the Aranga Quarry, New Zealand
  12. Scandio-winchite, ideally□(NaCa)(Mg4Sc)(Si8O22)(OH)2: The first Sc-dominant amphibole-supergroup mineral from Jordanów Śląski, Lower Silesia, southwestern Poland
  13. Znucalite, the only known zinc uranyl carbonate: Its crystal structure and environmental implications
  14. Presentation of the Dana Medal of the Mineralogical Society of America for 2023 to Razvan Caracas
  15. Acceptance of the Dana Medal of the Mineralogical Society of America for 2023
  16. Presentation of the Distinguished Public Service Award of the Mineralogical Society of America for 2024 to Sharon Tahirkheli
  17. Acceptance of the Distinguished Public Service Award of the Mineralogical Society of America for 2024
  18. Presentation of the Mineralogical Society of America Award for 2023 to Shaunna M. Morrison
  19. Acceptance of the Mineralogical Society of America Award for 2023
  20. Presentation of the 2023 Roebling Medal of the Mineralogical Society of America to Georges Calas
  21. Acceptance of the 2023 Roebling Medal of the Mineralogical Society of America
  22. Book Review
  23. Book Review: Cosmochemistry
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